Composition with surface modifying properties

ABSTRACT

The present invention refers to an aqueous composition comprising one or more amphoteric, organic polynitrogen-compounds having at least 3 nitrogen atoms contained in the molecule in the form of an amine and/or amide and one or more types of inorganic nanoparticles, a concentrate comprising said composition and to a method for treating and/or cleaning a surface which uses said composition.

The present invention relates to an aqueous composition which may beapplied in a method for cleaning and/or treating a surface, inparticular a hard surface.

When cleaning or treating surfaces, in particular hard surfaces, besidesa good cleaning performance it generally is desired to obtain thecleaned or treated surface with the lowest effort, in particular withoutthe requirement to dry or polish it. Moreover, the cleaned or treatedsurface should not show any unfavorable residues remaining on thesurface after the cleaning or treatment process like water spots,stripes or reams.

There are a lot of surfaces, often hard surfaces, which are regularlycontacted with water in larger amounts or which are cleaned or treatedvery frequently, often several times a day, like surfaces (floors orwalls) in public baths, in communal showers for example in companies,factories or gymnasiums. In a lower extent this also refers for exampleto a bathroom, and in particular the shower, or surfaces in the kitchenof a private household and even to the dishware in a dishwasher. Inaddition outdoor surfaces, and particularly windows, are also oftencontacted frequently with water, mainly in the form of rain or snow. Itis desired that when cleaning or treating such surfaces and preferablyalso when the surface gets into contact with larger amounts of waterafter having finished the cleaning or treatment process, the surfaceshould dry very fast, preferably even without further wiping, theoccurrence of water spots after the drying should be minimized, inparticular glass surfaces should be shining without stripes or reams andthe re-soiling should be reduced combined with a facilitated cleaning insubsequent cleaning procedures.

The undesired residues remaining on the surface after its cleaning anddrying may result from the soiling which originally has been on thesurface, from the water used for cleaning like from the water hardnessor contaminants dissolved in the water, from one or more componentscontained in the cleaning agent and/or from reaction products of any ofthe aforementioned sources.

In the state of the art several approaches are described to fulfill theabove mentioned requirements. In particular it can be distinguishedbetween a hydrophobizing and a hydrophilizing treatment of the surfaceand between a permanent or non-permanent treatment.

EP 1 215 276 A1 discloses washing and cleaning detergents comprisingmicrodisperse, hydrophilic silicate containing particles preferablyhaving a particle size of from 1 to 500 nm, and optionally comprising ahydrophobizing agent. The silicate containing particles are consideredto form a surface coating which replaces the soiling on the surface and,thereby, are supposed to facilitate the cleaning and to reduce there-soiling. The addition of hydrophobizing agents is supposed to improvethe effect of the silicate containing particles, since a correspondingcoating of the hydrophobizing agents enhances the soil removal andreduces the re-soiling.

U.S. Pat. No. 6,846,512 B2 points out that the water on suchhydrophobically modified surfaces will bead up. However, it is believedthat the beading of water may actually increase the formation of waterspots since the beads of water will leave deposits on the surface whenthey dry. Therefore, this document discloses a composition impartinghydrophilizing properties to a surface and its application for cleaningand/or treating the surface of vehicles. The cleaning compositionpreferably comprises a polymer which is supposed to render the surfacesemi-durably hydrophilic which means the surface modification ismaintained only for at least one rinse with water. In contrast theretothe treating composition comprises nanoparticles which show a longerlived effect.

A similar effect of nanoparticles is also described in US 2002/0172773A1. This document refers to rinse aid surface coatings comprising ananoparticle system and employing the same to impart surface modifyingproperties for all types of dishware surfaces in automatic dishwashingapplications. The surface modification caused by the non-photoactivenanoparticle coating can produce durable, protective, long lasting orsemi-permanent multi-use benefits. The surface coated with a layer ofnanoparticles can be further provided with a further polymer layerapplied thereupon which may impart for example hydrophilic orhydrophobic properties to the coated surface.

However, in particular long lasting and especially permanent effectscaused by such coatings may be disadvantageous when the properties ofthe coatings change during use. If this is the case it might be verydifficult to regain the original properties of the surface beforeapplication of the coating or even the initial properties of thecoating. This is of particular relevance in case repeated application ofthe permanent coating does not result in the same properties of thecoating as were achieved by the first coating.

WO 2004/055145 A1 also uses nanoparticles, namely colloidal silica sol,to impart hydrophilic properties to a surface, which are supposed to besemi-permanent, i.e. they occur for some weeks after the treatment ofthe surface, but are not permanent.

Although when using some of the above mentioned compositions ahydrophilization of the cleaned or treated surface may be achieved whichresults in an improved wetting of the treated surface and, therefore, ina reduced amount of water spots compared to the untreated surface, therestill is a need to provide further compositions with a still improveddrying performance, a reduced re-soiling and facilitated re-cleaningproperties with an at least not deteriorated overall cleaningperformance.

The above need is satisfied by providing an aqueous compositioncomprising one or more amphoteric, organic polynitrogen-compounds havingat least 3 nitrogen atoms contained in the molecule in the form of anamine and/or amide and one or more types of nanoparticles on aninorganic basis.

Surprisingly, the inventor of the present invention have found out, thata combination of components as mentioned above leads to an improvedperformance compared to compositions in which at least one of thecomponents are missing. Surfaces, and in particular hard surfaces,treated with a corresponding composition show an increasedhydrophilicity of the surface. By the term “hydrophilicity” it is meantthat the surface has a high affinity for water. Thus, treating orcleaning a surface with such a composition increases the affinitybetween water and the surface compared to the untreated surface.Thereby, water spreads out on the surface to maximize the contact,providing a water film on the surface which may run down on inclinedsurfaces.

Typically, the amount of liquid remaining on a hydrophobized surface islarger than the amount of liquid remaining on a hydrophilized surface.Thus, whereas, water beads forming on hydrophobized surfaces may resultin lots of separated water spots after drying the, in most cases, thelittle residues which may remain on the surface resulting from a part ofthe water film which didn't run down are more continuous and attractless attention.

In addition, treating or cleaning a surface with the above specifiedcomposition results in a good overall cleaning performance and in afacilitated cleaning in the next cleaning procedure.

A main component in the composition according to the present inventionrepresents one or more types of nanoparticles. Nanoparticles which aresuitable for use in the present composition preferably have an averageparticle size of from 1 to 50 nm, preferably of from 2 to 40 nm and morepreferred of from 4 to 20 nm.

The BET surface area for those particles preferably lies in the range offrom 50 to 450, more preferred of from 200 to 400 and most preferred offrom 300 to 380 m²/g (as determined according to DIN 66131).

In the composition according to the present invention the one or moretypes of nanoparticles preferably are selected from metal oxides,inorganic silicon compounds, carbonates and hydroxides.

Examples for suitable metal oxides representing suitable compounds forthe formation of nanoparticles are aluminum oxide, zirconium oxide,titanium oxide, cerium oxide, zinc oxide and mixtures thereof.

However, it is preferred to select the one or more types ofnanoparticles from the group comprising amorphous silicon dioxide,silicates, alumosilicates, silica sols, fumed silica or mixturesthereof.

Further suitable nanoparticles which may be used in the presentinvention are for example described in US 2002/0172773 A1. This documentteaches that beside oxides, silicates, carbonates and hydroxides somelayered clay minerals and inorganic metal oxides can be used asnanoparticles including hydrophilic surface properties.

The inorganic metal oxides can be exemplified by silica- oralumina-based nanoparticles that are naturally occurring or synthetic.Aluminum can be found in many naturally occurring sources, such askaolinite and bauxite. The naturally occurring sources of alumina areprocessed by the Hall process or the Bayer process to yield the desiredalumina type required. Various forms of alumina are commerciallyavailable in the form of Gibbsite, Diaspore, and Boehmite frommanufactures such as Condea.

Suitable layered clay minerals include those in the geological classesof the smectites, the kaolins, the illites, the chlorites, theattapulgites and the mixed layer clays. Typical examples of specificclays belonging to these classes are the smectites, kaolins, illites,chlorites, attapulgites and mixed layer clays. Smectites, for example,include montmorillonite, bentonite, pyrophyllite, hectorite, saponite,sauconite, nontronite, talc, beidellite, volchonskoite and vermiculite.Kaolins include kaolinite, dickite, nacrite, antigorite, anauxite,halloysite, indellite and chrysotile. Illites include bravaisite,muscovite, paragonite, phlogopite and biotite. Chlorites includecorrensite, penninite, donbassite, sudoite, pennine and clinochlore.Attapulgites include sepiolite and polygorskyte. Mixed layer claysinclude allevardite and vermiculitebiotite. Variants and isomorphicsubstitutions of these layered clay minerals offer unique applications.

The layered clay minerals may be either naturally occurring orsynthetic. Natural or synthetic hectorites, montmorillonites andbentonites may as well be used as hectorites clays commerciallyavailable. Typical sources of commercial hectorites are the LAPONITESfrom Southern Clay Products, Inc., U.S.A.; Veegum Pro and Veegum F fromR. T. Vanderbilt, U.S.A.; and the Barasyms, Macaloids and Propaloidsfrom Baroid Division, National Read Comp., U.S.A.

Natural clay minerals which may be used typically exist as layeredsilicate minerals and less frequently as amorphous minerals. A layeredsilicate mineral has SiO₄ tetrahedral sheets arranged into atwo-dimensional network structure. A 2:1 type layered silicate mineralhas a laminated structure of several to several tens of silicate sheetshaving a three layered structure in which a magnesium octahedral sheetor an aluminum octahedral sheet is sandwiched between two sheets ofsilica tetrahedral sheets.

A sheet of an expandable layer silicate has a negative electric charge,and the electric charge may be neutralized by the existence of alkalimetal cations and/or alkaline earth metal cations. Smectite orexpandable mica can be dispersed in water to form a sol with thixotropicproperties. Further, a complex variant of the smectite type clay can beformed by the reaction with various cationic organic or inorganiccompounds. As an example of such an organic complex, an organophilicclay in which a dimethyldioctadecyl ammonium ion (a quaternary ammoniumion) may be introduced by cation exchange and has been industriallyproduced and used as a gellant of a coating.

As to synthetic clays, with appropriate process control, the processesfor the production of synthetic nanoscale powders (i.e. synthetic clays)does indeed yield primary particles, which are nanoscale. However, theparticles are not usually present in the form of discrete particles, butinstead predominantly assume the form of agglomerates due toconsolidation of the primary particles. Such agglomerates may reachdiameters of several thousand nanometers, such that the desiredcharacteristics associated with the nanoscale nature of the particlescannot be achieved. The particles may be deagglomerated, for example, bygrinding as described in EP-A 637,616 or by dispersion in a suitablecarrier medium, such as water or water/alcohol and mixtures thereof.

An example of a suitable substituted variant of lithium magnesiumsilicate is where the hydroxyl group is partially substituted withfluorine. Lithium and magnesium may also be partially substituted byaluminum. In fact, the lithium magnesium silicate may be isomorphicallysubstituted by any member selected from the group consisting ofmagnesium, aluminum, lithium, iron, chromium, zinc and mixtures thereof.

Synthetic hectorite is commercially marketed under the trade nameLAPONITE™ by Southern Clay Products, Inc. There are many grades orvariants and isomorphous substitutions of LAPONITE™ marketed. Examplesof commercial hectorites are Lucentite SWN™, LAPONITE S™, LAPONITE XLS™,LAPONITE RD™, LAPONITE B™ and LAPONITE RDS™. LAPONITE XLS™ has thefollowing characteristics: analysis (dry basis) SiO₂ 59.8%, MgO 27.2%,Na₂O 4.4%, Li₂O 0.8%, structural H₂O 7.8%, with the addition oftetrasodium pyrophosphate (6%); specific gravity 2.53; bulk density 1.0.Generally LAPONITE™ has the formula:[Mg_(w)Li_(x)Si₈O₂₀OH_(4-y)F_(y)]^(z-)wherein w=3 to 6, x=0 to 3, y=0 to 4, z=12-2w-x, and the overallnegative lattice charge may be balanced by counter-ions; and wherein thecounter-ions are selected from the group consisting of selected Na⁺, K⁺,NH₄ ⁺, Cs⁺, Li⁺, Mg⁺⁺, Ca⁺⁺, Ba⁺⁺, N(CH₃)₄ ⁺ and mixtures thereof.

Fumed silica may also be used, preferably in powdered form, in thecomposition according to the present invention is also commerciallyavailable in the form of its nanoparticles like under the trade nameAEROSIL® 90, 130, 150, 200, 300 and 380, supplied by Degussa

However, in a particular preferred embodiment colloidal, nanoparticulatesilica sols are contained in the composition according to the presentinvention. A colloidal nanoparticulate silica sol in the sense of thepresent invention represents a stable mainly aqueous dispersion ofamorphous, particulate silicon dioxide SiO₂ having the above specifiedaverage particle sizes. This means that the particles are small enoughthat gravity doesn't cause them to settle, but large enough not to passthrough a membrane.

Corresponding silica sol nanoparticles are commercially available, forexample supplied by Eka Chemicals/Akzo under the trade name Bindzil®30/360 having an average particle size of 9 nm. Further appropriatesilica sols can be exemplified by Bindzil® 15/500, 30/220, 40/220,305/220, which are all supplied by Eka Chemicals/Akzo, Nyacol® 215, 830,1430, 2034DI and Nyacol® DP5820, DP5480, DP5540 and correspondingNyacol® products, supplied by Nyacol® Products, Levasil® 100/30,100F/30, 100S/30, 200/30, 200F/30, 300F/30, VP 4038, VP 4055, suppliedby H.C. Starck/Bayer) as well as by CAB-O-Sperse® PG 001, PG 002(aqueous dispersion of CAB-O-SIL® supplied by Cabot, Quarton PL-1, PL-3,supplied by FusoChemical Co., and Köstrosol 0830, 1030, 1430 supplied byChemiewerk Bad Köstritz.

In some compositions it might be helpful to use a silica sol in whichthe surface of the colloidal silica nanoparticles is modified. Suitablemodifications of the surface of the silica nanoparticles representsilanizing, an alumina-modification and a coating with aluminium oxide.The surface of colloidal silica particles typically is anionic at analkaline pH level. It can be stabilized with cations like sodium orammonium.

However, generally the presence of acids in a composition comprisingcolloidal silica sols leads to the formation of silica gels, which ofcourse is not desired. Therefore, for use in acidic conditions silicasols may be used in which trivalent aluminium atoms are substituted fora part of the tetravalent silicon atoms in the surface of the particles.This creates a fixed negative charge which is independent of pH.Therefore, the stability of the alumina-modified sols will increasecontinuously with decreasing pH. Such modified silica sols arecommercially available under the trade name Bindzil® 257/360 which issupplied by Akzo.

A coating of the silica nanoparticles with a layer of aluminium oxideconverts the surface charge from negative to positive. Such cationiccolloidal silicas typically are colloidal dispersions of discretespherical silica particles in weakly acidic water. The interior of theparticles preferably is mainly formed of pure amorphous silicon dioxide.The surface of the particles is modified with inorganic compounds likealuminium oxide to give them a cationic surface charge. Such modifiedsilica sols are commercially available under the trade name Bindzil®CAT, CAT 220 and CAT 80 which are all supplied by Akzo.

Further suitable silica sols having a silica surface modificationrepresent a silica sol in which the surface of the silica particles issilanized. Corresponding silica sols generally have a silica content ofat least 20 wt. % based on the total sol and a weight ratio of silane tosilica of from 0.003 to about 2. Suitable silanes for modifying thesurface of the silica particles are exemplified by tris-(trimethoxy)silane, octyl triethoxysilane, methyl triethoxysilane, methyltrimethoxysilane; isocyanate silane such astris-[3-(trimethoxysilyl)propyl] isocyanurate; gamma-mercaptopropyltrimethoxysilane,bis-(3-[triethoxysilyl]propyl) polysulfide,beta-(3,4-epoxycyclohexyl)-ethyl trimethoxysilane; silanes containing anepoxy group (epoxy silane), glycidoxy and/or a glycidoxypropyl groupsuch as gamma-glycidoxypropyl trimethoxysilane,gamma-glycidoxypropylmethyldiethoxysilane, (3-glycidoxypropyl)trimethoxy silane, (3-glycidoxypropyl)hexyltrimethoxysilane,beta-(3,4-epoxycyclohexyl)-ethyltriethoxysilane; silanes containing avinyl group such as vinyltriethoxysilane, vinyl trimethoxysilane, vinyltris-(2-methoxyethoxy)silane, vinyl methyldimethoxysilane, vinyltriisopropoxysilane; gamma-methacryloxypropyl trimethoxysilane,gamma-methacryloxypropyl triisopropoxysilane, gamma-methacryloxypropyltriethoxysilane, octyltrimethyloxy silane, ethyltrimethoxy silane,propyltriethoxy silane, phenyltrimethoxy silane,3-mercaptopropyltriethoxy silane, cyclohexyltrimethoxy silane,cyclohexyltriethoxy silane, dimethyldimethyoxy silane,3-chloropropyltriethoxy silane, 3-methacryoxypropyltrimethoxy silane,i-butyltriethoxy silane, trimethylethoxy silane, phenyldimethylethoxysilane, hexamethyidisiloxane, trimethylsilyl chloride, vinyltriethoxysilane, hexamethyldisilizane, and mixtures thereof. U.S. Pat. No.4,927,749 discloses further suitable silanes which may be used in thepresent invention. The most preferred silanes, however, are epoxysilanes and silanes containing a glycidoxy or glycidoxypropyl group,particularly gamma-glycidoxypropyltrimethoxysilane and/or gammaglycidoxypropyltmethyldiethoxysilane.

Such silane-modified silica sols are commercially available from EkaChemicals/Akzo under the trade name Bindzil® CC30 and CC40, with anaverage particle size of 7 nm and 12 nm, respectively.

Although it is also possible to use a mixture of any of the abovedescribed types of nanoparticles, like a combination of nanoparticles ofthe Laponite™ type and a colloidal silica sol, for example, and also ofvarious nanoparticles of the same type, like a mixture of severalBindzil® silica sols, for example, it is most preferred to use only onetype of nanoparticles and with no variation within this type.

The one or more inorganic nanoparticles are preferably contained in atotal amount of from 0.01 to 3 wt. %, preferably of from 0.1 to 1.5 wt.%, more preferred of from 0.3 to 0.7 wt. % and most preferred of from0.5 to 0.6 wt. % based on the total composition. Analogous to what wasmentioned before the amounts refer to the amounts of the activesubstance. In case commercially available products are employed whichare diluted for example with water this has to be taken into account.Moreover the amounts refer to the end use composition. This especiallyshould be born in mind in case a concentrate is prepared and not the usesolution.

As to the concentrate the nanoparticles preferably are contained thereinin a total amount of from 0.05 to 15 wt. %, preferably of from 0.5 to 10wt. % and more preferred of from 1.2 to 6 wt. %.

The third group of the main components of the composition according tothe pre-sent invention represents the amphoteric organicpolynitrogen-compound. Organic polynitrogen compound in the sense of thepresent invention means an organic compound comprising at least 3nitrogen atoms which are contained in the molecule in the form of anamine, like a primary, a secondary or a teriary amine, and/or in theform of an amide. By amphoteric is meant that the same compound mayfunction as acceptor as well as a donator for protons.

Suitable functional groups imparting proton donator properties representcarboxy residues or derivatives thereof, like amides, anhydrides oresters, as well as salts thereof, like alkali salts, for example sodiumor potassium salts, or ammonium salts, which may be converted into thecarboxy group.

Depending on the size of the polynitrogen moiety there may be one ormore proton donating functionalities in the molecule. It is preferredthat more than one proton donating functionalities are present in theamphoteric polynitrogen compound.

In a preferred embodiment the amphoteric organic polynitrogen compoundis a polymeric amphoteric organic polynitrogen-compound. This means itpreferably has an average molecular weight of at least 300.

The one or more amphoteric organic polynitrogen compounds preferably areindependently obtainable from reacting

-   -   Polyalkylene polyamines, polyamidoamines, ethyleneimine-grafted        polyamidoamides, polyetheramines or mixtures thereof as        component A    -   optionally with at least bi-functional cross-linking agents        having a functional group independently selected from a        halohydrin, a glycidyl, an aziridine or an isocyanate moiety or        a halogen atom, as component B, and with monoethylenically        unsaturated carboxylic acids; salts, esters, amides or nitriles        of monorethylenically unsaturated carboxylic acids; salts,        esters, amides or nitriles of monoethylenically unsaturated        carboxylic acids, chlorocarboxylic acids and/or glycidyl        compounds like glycidyl acid, glycidyl amide or glycidyl esters.

Those compounds are described for example in WO 2005/073357 A2. Theamphoteric organic polynitrogen compounds are obtainable by reactingcomponents A, optionally with B and with C. The compound therefore canbe present in cross-linked or uncross-linked form, wherein component Ain any case is modified with component C.

Components A, optionally B and C may be used in any possible ratio. Ifcomponent B is employed, preferably components A and B are used in amolar ratio of from 100:1 to 1:1000, more preferred of from 20:1 to1:20. The molar ratio of components A and C preferably is chosen suchthat the molar ratio of the hydrogen atoms bonded to the nitrogen in Aand component C is from 1:0.2 to 1:0.95, more preferred from 1:0.3 to1:0.9, and even more preferred from 1:0.4 to 1:0.85.

Component A

Suitable compounds as component A represent polyalkylene polyamines.Herein polyalkylene polyamines are meant to refer to compoundscomprising at least 3 nitrogen atoms, like diethylenetriamine,triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexamine,diaminopropylenediamine, trisaminopropylamine and polyethyleneimine.Polyethyleneimines preferably have an average molecular weight (M_(w))of at least 300. It is particularly preferred that the average molecularweight of the polyethyleneimines ranges from 800 to 2,000,000, morepreferred from 20,000 to 1,000,000, and even more preferred from 20,000to 750,000, as determined by means of light scattering.

The polyethyleneimines may be partially amidated. Products of this kindare obtainable by reacting polyalkylene polyamines with carboxylicacids, carboxylic acid esters, carboxylic acid anhydrides oracylhalides. The polyalkylene polyamines as suitable in the presentinvention preferably are amidated to an extent of 1 to 30, morepreferred of up to 20% for the subsequent reactions. The amidatedpolyalkylene polyamines are required to contain free NH-groups in orderto let them react with compounds B and C. Suitable carboxylic acidswhich may be used to amidate the polyalkylene polyamines are exemplifiedby C₁-C₂₈ carboxylic acids, like formic acid, acetic acid, propionicacid, benzoic acid, lauric acid, palmitic acid, stearic acid, oleicacid, linoleic acid and behenic acid. It is also possible to amidate byreacting the polyalkylene polyamine with alkyldiketene.

Moreover, the polyalkylene polyamines may be used partly in quaternizedform as component A. Suitable quaternization agents represent forexample alkyl halides, like methyl chloride, ethyl chloride, butylchloride, epichlorohydrin, hexyl chloride, dimethyl sulfate, diethylsulfate and benzyl chloride. If quaternized polyalkyleneamines are usedas component A the degree of quaternization preferably is 1 to 30, morepreferred up to 20%.

Further compounds which are appropriate as component A arepolyamidoamines. Polyamidoamines are obtainable, for example, byreacting C₄-C₁₀ dicarboxylic acids with polyalkylene polyaminescontaining preferably 3 to 10 alkaline nitrogen atoms. Suitabledicarboxylic acids can be exemplified by succinic acid, maleic acid,adipic acid, glutaric acid, suberic acid, sebacic acid and terephthalicacid. It is also possible to use mixtures of carboxylic acids, like amixture of adipic acid and glutaric acid, or maleic acid and adipicacid. Preferably adipic acid is used to produce the polyamidoamines.Suitable polyalkylene polyamines which may be condensed with thedicarboxylic acids are similar to the ones mentioned above, and can beexemplified by diethylenetriamine, triethylenetetraamine,dipropylenetriamine, tripropylenetetraamine, dihexamethylenetriamine,aminopropyl ethylenediamine and bis-aminopropyl ethylenediamine.Mixtures of polyalkylene polyamines may also be used to preparepolyamidoamines. Preferably the preparation of the polyamidoamines takesplace in substance, however optionally the preparation can be carriedout in inert solvents. The condensation reaction of the dicarboxylicacids with the polyalkylene polyamines is carried out at elevatedtemperatures like in the range of from 120 to 220° C. The water formedduring the reaction is distilled off the reaction mixture. Lactones orlactams derivable from carboxylic acids having 4 to 8 carbon atoms alsomay be present during the condensation reaction. Generally, 0.8 to 1.4mole of polyalkyleneamines are used with each mole of dicarboxylic acid.The thus obtained polyamidoamines have primary and secondary NH-groupsand are soluble in water.

A further compound which is suitable as component A represents anethyleneimine-grafted polyamidoamine. Such products are obtainable byreacting ethyleneimine with the above described polyamidoamines in thepresence of Brönstedt-acids or Lewis-acids, like sulfuric acid,phosphoric acid or boron trifluoride etherate. Those conditions resultin a graft of ethyleneimine to the polyamidoamine. For example eachalkaline nitrogen group of the polyamidoamine may be grafted with 1 to10 ethyleneimine units, i.e. 10 to 500 parts by weight of ethyleneimineare used with 100 parts by weight of a polyamidoamine.

In addition polyetheramines represent appropriate compounds as componentA. Such compounds are known for example from DE-A 29 16 356.Polyetheramines are obtainable from condensing diamines and polyamineswith chlorohydrin ethers at elevated temperatures. The polyamines maycomprise up to 10 nitrogen atoms. The chlorohydrin ethers themselves canbe prepared for example by reacting a dihydric alcohol having 2 to 5carbon atoms, the alkoxylation products thereof having up to 60alkyleneoxide units, glycerol or polyglycerol comprising up to 15glycerol units, erythritol or pentaerythritol with epichlorohydrin. Atleast 2 to 8 moles of epichlorohydrin are reacted with each mole of saidalcohol. The reaction of the diamines and the polyamines on one hand andthe chlorohydrin ethers on the other hand generally takes place attemperatures of from 1 to 200° C., preferably of from 110 to 200° C.Moreover, polyetherpolyamines may be prepared by condensingdiethanolamine or triethanolamine according to the methods known in theart, as the ones disclosed in U.S. Pat. No. 4,404,362, U.S. Pat. No.4,459,220 and U.S. Pat. No. 2,407,895.

It is particularly preferred to use polyalkylene polyamines as componentA, which optionally are amidated to a degree of 20% at most. Morepreferred compounds represent polyalkylene polyamines, especiallypolyethyleneimines, which have an average molecular weight of from 800to 2,000,000, more preferred of from 200,000 to 1,000,000, and mostpreferred of from 20,000 to 750,000 in a particularly advantageousembodiment.

Component B

Suitable compounds for use as component B represent bifunctionalcross-linking agents comprising halohydrin units, glycidyl units,aziridine units or isocyanate units or a halogen atom as functionalgroups.

Suitable cross-linking agents can be exemplified by epihalohydrin,preferably epichlorohydrin, as well as α,ω-bis-(chlorohydrin)polyalkylene glycol ether and the α,ω-bis-(epoxides) of polyalkyleneglycol ethers which are obtainable therefrom by treatment with bases.The chlorohydrinethers may be prepared, for example, by reactingpolyalkylene glycols with epichlorohydrin in a molar ratio of 1 to atleast 2 to 5. Appropriate polyalkylene glycols represent polyethyleneglycol, polypropylene glycol and polybutylene glycol as well as blockcopolymers of C₂- to C₄ alkyleneoxides. The average molecular weight(M_(w)) of the polyalkylene glycols generally ranges from 100 to 6000,preferably from 300 to 2000 g/mol. α,ω-bis(chlorohydrin) polyalkyleneglycol ether are for example described in U.S. Pat. No. 4,144,123. Thisdocument also discloses that the corresponding bisglycidylethers of thepolyalkylene glycols result from dichlorohydrinethers by treatment withbases.

Moreover, α,ω-dichloropolyalkylene glycols are suitable as cross-linkingagents, like the ones disclosed in EP-A 0 025 515. Thoseα,ω-dichloropolyalkylene glycols are obtainable by reacting dihydric totetrahydric alcohols, preferably alkoxylated dihydric to tetrahydricalcohols either with thionyl chloride resulting in a cleavage of HClfollowed by catalytic decomposition of the chlorosulfonated compoundwhile eliminating sulfur dioxide, or with phosgene resulting in thecorresponding bischlorocarbonic acid ester while eliminating HCl, whichbischlorocarbonic acid esters are catalytically decomposed eliminatingcarbondioxid to result in α,ω-dichloro ether.

Preferably the dihydric to tetrahydric alcohols are ethoxylated and/orpropoxylated glycols wherein each mole of glycol is reacted with 1 to100, in particular with 4 to 40 moles of ethylene oxide.

α,ω- or vicinal dichloroalkanes, like 1,2-dichloroethane,1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane and1,6-dichlorohexane represent other appropriate cross-linking agents. Itis also possible to use cross-linking agents which are obtainable fromreacting at least trihydric alcohols with epichlorohydrin, resulting inreaction products having at least two chlorohydrin-moieties. Examplesfor polyhydric alcohols are glycerol, ethoxylated or propoxylatedglycerol, polyglycerol having 2 to 15 glycerol units within the moleculeand optionally ethoxylated and/or propoxylated polyglycerol.Cross-linking agents of t his kind are known for example from DE-A 29 16356. Other appropriate cross-linking agents represent cross-linkingagents containing blocked isocyanate groups for exampletrimethylhexamethylene diisocyanate blocked with2,2,3,6-tetramethylpiperidone-4. Such cross-linking agents are known forexample from DE-A 40 28 285. Moreover, cross-linking agents based onpolyethers or substituted hydrocarbons containing aziridine moietieslike 1,6-bis-N-aziridinohexane are suitable as cross-linking agents.According to the present invention the cross-linking agents may beemployed individually or as a mixture of two or more cross-linkingagents.

It is particularly preferred to use epihalohydrins, especiallyepichlorohydrin, α,ωbis-(chlorohydrin) polyalkylene glycol ether,α,ω-bis-(epoxides) of polyalkylene glycol ethers and/orbisglycidylethers of polyalkylene glycols as component B.

Component C

Examples for compounds suitable as component C representmonoethylenically unsaturated carboxylic acids having preferably 3 to 18carbon atoms in their alkenyl residue. Appropriate monoethylenicallyunsaturated carboxylic acids include by acrylic acid, methacrylic acid,diemethacrylic acid, ethyl acrylic acid, allyl acetic acid, vinyl aceticacid, maleic acid, fumaric acid, itaconic acid, methylene malonic acid,oleic acid and linoleic acid. Monoethylenically unsaturated carboxylicacids selected from the group comprising acrylic acid, methacrylic acidand maleic acid are especially preferred.

It is also possible to use the salts of the aforementionedmonoethylenically unsaturated carboxylic acids as component C. Suitablesalts generally represent alkali metal, alkaline earth metal andammonium salts of the aforementioned acids. Particularly preferred aresodium, potassium and ammonium salts. Ammonium salts can be derived fromammonia as well as from amines or amine derivatives like ethanolamine,diethanolamine and triethanolamine. Examples for alkaline earth metalsalts generally represent magnesium and calcium salts of theaforementioned monoethylenically unsaturated carboxylic acids.

Suitable esters of the aforementioned monoethylenically unsaturatedcarboxylic acids are derivable from monohydric C₁-C₂₀ alcohols or fromdihydric C₂-C₆ alcohols. Esters which may be used herein can beexemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate,isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methylmethacrylate, ethyl methacrylate, isopropyl methacrylate, n-butylmethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, palmitylacrylate, lauryl acrylate, diaryl acrylate, lauryl methacrylate,palmityl methacrylate, stearyl methacrylate, dimethyl maleate, diethylmaleate, isopropyl maleate, 2-hydroxyethyl acrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate,2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, hydroxybutylacrylate, hydroxybutyl methacrylate and hydroxyhexyl acrylate andhydroxyhexyl methacrylate.

Acrylamide, methacrylamide and oleic amide represent appropriate amidesof monoethylenically unsaturated carboxylic acids. Suitable nitriles ofthe monoethylenically unsaturated carboxylic acids are acrylonitrile andmethacrylonitrile. It is also possible to use amides which are derivableby reacting monoethylenically unsaturated carboxylic acids, inparticular (meth)acrylic acid, with amidoalkane sulfonic acids. Thoseamides are especially advantageous which are obtainable from reactingmonoethylenically unsaturated carboxylic acids, especially (meth)acrylicacid, with amidoalkane sulfonic acids, as represented by formulae I orII:H₂C═CH—X—SO₃H  (I)H₂C═C(CH₃)—X—SO₃H  (II)wherein X either is not present or a spacing group of the formulae—C(O)—NH—CH₂—_(n)(CH₃)_(n)(CH₂)_(m)—, —C(O)NH—, —C(O)—NH—(CH(CH₃)CH₂)—or —C(O)—NH—CH(CH₂CH₃)—, with n being 0 to 2 and m being 0 to 3.Particularly preferred are 1-acrylamido-1-propanesulfonic acid(X═—C(O)—NH—CH(CH₂CH₃)— in formula I), 2-acrylamido-1-propanesulfonicacid (X═(O)—NH—(CH(CH₃)CH₂)— in formula I),2-acrylamido-2-methyl-1-propanesulfonic acid (—C(O)—NH—C(CH₃)₂(CH₂)— informula I), 2-methacrylamido-2-methyl-1-propanesulfonic acid(X═—C(O)—NH—C(CH₃)₂(CH₂)— in formula II) and vinylsulfonic acid (X notpresent in formula I).

Moreover chlorocarboxylic acids are appropriate as component C. Suchchlorocarboxylic acids include chloroacetic acid, 2-chloropropionicacid, 2-chlorobutanoic acid, dichloroacetic acid and 2,2′-dichloropropionic acid.

Further compounds suitable as component C are glycidyl compounds whichare represented by the following formula:

whereinX NH₂, OMe, ORMe H, Na, K, ammonium andR C₁-C₄ alkyl or C₂-C₄ hydroxyalkyl.

Preferred compounds of formula III represent glycidyl acid, sodium,potassium, ammonium, magnesium or calcium salts thereof, glycidyl amideand glycidyl ester like glycidyl methyl ester, glycidyl ethyl ester,glycidyl n-propyl ester, glycidyl n-butyl ester, glycidyl iso-butylester, glycidyl-2-ethylhexyl ester, glycidyl-2-hydroxypropyl ester andglycidyl-4-hydroxybutyl ester. Glycidyl acid and sodium, potassium orammonium salts thereof or glycidyl amide are particularly preferred.

It is particularly advantageous to use a monoethylenically unsaturatedcarboxylic acid as component C, especially acrylic acid, methacrylicacid or maleic acid, and more preferred acrylic acid.

The above described preferred amphoteric organic polynitrogen compoundscan be produced according to methods known in the art. Suitable methodsof production are disclosed for example in DE-A 42 44 194, in whichcomponent A at first reacts with component C and afterwards component Bis added. According to DE-A 42 44 194 it is also possible to havecomponents C and B reacted simultaneously with component A.

In a preferred embodiment the amphoteric organic polynitrogen compoundscomprising components A, B and C are prepared using a method comprisingthe steps:

-   -   i) cross-linking of polyalkylene polyamines, polyamidoamines,        ethyleneimine-grafted polyaminoamides, polyetheramines or        mixtures thereof as component A with at least bifunctional        cross-linking agents having a functional group independently        selected from a halohydrin, a glycidyl, an aziridine or an        isocyanate moiety or a halogen atom, as component B, and    -   j) reacting the product obtained in step i) with        monoethylenically unsaturated carboxylic acids; salts, esters,        amides or nitriles of monoethylenically unsaturated carboxylic        acids, chlorocarboxylic acids and/or glycidyl compounds like        glycidyl acid, glycidyl amide or glycidyl esters as component C.        Step i)

The cross-linking of the compounds exemplified for component A with thecross-linking agents C proceeds according to methods known to theskilled person. Generally, the cross-linking is carried out at atemperature of from 10 to 200° C., preferably of from 30 to 100° C. andtypically at standard pressure. The reaction times depend on the usedcomponents A and B and in most cases range from 0.5 to 20 hours,preferably from 1 to 10 hours. In general, curing component B is addedin the form of an aqueous solution to have the reaction take place inaqueous solution as well. The product obtained can be isolated ordirectly used in step j) without further isolation which is preferred.

Step j)

In step j) the product obtained in step i) is reacted with the compoundaccording to group C. If the compound of group C comprises amonoethylenically unsaturated compound having a double bonding systemthe primary or secondary amine groups of the cross-linked productobtained in step i) are added to the free end of the double bond similarto a Michael-addition. If the compound of group C is a chlorocarboxylicacid or a glycidyl compound of formula I the reaction of the aminemoieties proceeds at the chloro group or the epoxy group. The reactiontypically is carried out at a temperature of from 10 to 200° C.,preferably of from 30 to 100° C. and usually at standard pressure. Thereaction time depends on the components used and generally lies withinthe range of from 0.5 to 100 hours, preferably from 1 to 50 hours.

It is common to carry out the reaction in an aqueous solution whereinthe product obtained in step i) already is present in an aqueoussolution.

Specific examples for the preparation of such compounds are alsodescribed in WO 2005/073357 A2.

One particularly preferred compound of the amphoteric organicpolynitrogen compounds as specified above, which may be used in thecomposition of the present invention is commercially available under thetrade name Sokalan® HP70, supplied by BASF.

Preferably the one or more amphoteric organic polynitrogen compounds arecontained in the composition in a total amount of from 0.01 to 3 wt. %,preferably of from 0.1 to 1.5 wt. %, more preferred of from 0.3 to 0.7wt. % and most preferred of from 0.5 to 0.6 wt. % based on the total enduse composition. Those amounts refer to the amount of the activesubstance. In case commercially available products are employed whichare diluted for example with water this has to be taken into account.Moreover the amounts refer to the end use composition. This especiallyshould be born in mind in case a concentrate is prepared and not the usesolution directly.

As to the concentrate the one or more amphoteric organic polynitrogencompounds preferably are contained therein in a total amount of from0.05 to 15 wt. %, preferably of from 0.5 to 10 wt. % and more preferredof from 1.2 to 6 wt. %.

Without being bound to this theory it is assumed that the one or moreamphoteric organic polynitrogen compounds provide some kind of adhesionbetween the nanoparticles and the surface to be treated and/or cleaned.This theory is strengthened by the observation that the surfacemicro-roughness of the surface to be treated or cleaned is increasedafter its treatment or cleaning. With surface micro-roughness is meantthe number which equals the mean deviation of the surface protrusionsfrom a hypothetical perfect surface. Generally, the surfacemicro-roughness is determined by means of atomic force microscopy (AFM)and is measured in nm or μm. After having used the composition accordingthe present invention the surface micro-roughness generally is increasedby 3 to 50 nm. Said increase approximately corresponds to the averageparticle size of the nanoparticles used and is independent from thesurface micro-roughness present before having treated the surface withthe composition of the present invention. This indicates that at leastsome of the nanoparticles are present on the outer surface, probablyembedded in the one or more amphoteric organic polynitrogen compoundswhich are at least to some extent coated on the surface. Therefore, theuse of the amphoteric organic polynitrogen compounds is considered tohelp to control the rinses with water or other liquids partly orcompletely dissolving the polynitrogen compounds or the number oftreatments after which the nanoparticles still adhere or no longeradhere to the treated surface. Thus, the selection of the amphotericorganic polynitrogen compound is supposed to influence whether or not anon-permanent adhesion is obtained.

Depending on the intended use of the composition it may be of advantageif the composition additionally comprises one or more surfactants. Thepresence of surfactants in the composition according to the presentinvention improves the wetting of the surface to be cleaned with thepresent composition. Those one or more surfactants used in thecomposition according to the present invention can be independentlyselected from anionic, nonionic, cationic, amphoteric and zwitterionicsurfactants.

The use of the surfactants may vary depending on the intended field ofapplication. However, in one preferred embodiment, in particular forcleaning glass or ceramic, tiles or similar materials, only one or moreanionic surfactants, one or more nonionic surfactants or mixturesthereof are used.

In case the pH value of the composition is below 7, as is usually thecase for example in bath cleaners, it turned out to be particularlyadvantageous if the composition does not contain any anionic surfactantsbut only one or more nonionic surfactants.

Preferably the composition according to the present invention comprisesat least one nonionic surfactant selected from the group of semi-polarnonionic surfactants. Generally, semi-polar nonionics are high foamersand foam stabilizers. The semi-polar nonionic surfactants include theamine oxides, phosphine oxides, sulfoxides and their alkoxylatedderivatives.

Amine oxides preferably are tertiary amine oxides corresponding to thegeneral formula:

wherein the arrow is a conventional representation of a semi-polar bond;and R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from 8 to 24 carbon atoms; R² and R³are alkyl or hydroxyalkyl of 1-3 carbon atoms or a mixture thereof; R²and R³ can be attached to each other, e.g. through an oxygen or nitrogenatom, to form a ring structure; R⁴ is an alkylene or a hydroxyalkylenegroup containing 2 to 3 carbon atoms; and n ranges from 0 to 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are decyldimethylamine oxide, dodecyldimethylamine oxide,tridecyldimethylamine oxide, tetradecyldimethylamine oxide,pentadecyldimethylamine oxide, hexadecyldimethylamine oxide,heptadecyldimethylamine oxide, octadecyldimethylamine oxide,dodecyldipropylamine oxide, tetradecyldipropylamine oxide,hexadecyldipropylamine oxide, tetradecyldibutylamine oxide,octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and R¹ is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to 24carbon atoms in chain length; and R² and R³ are each alkyl moietiesseparately selected from alkyl or hydroxyalkyl groups containing 1 to 3carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphineoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyidecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, from0 to 5 ether linkages and from 0 to 2 hydroxyl substituents; and R² isan alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Moreover, other common nonionic surfactants may also be used. Thosenonionic surfactants are generally characterized by the presence of anorganic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicoxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants in the present invention include:

1. Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available under the tradenames Pluronic® and Tetronic® manufactured by BASF Corp.

Pluronic® compounds are difunctional (two reactive hydrogens) compoundsformed by condensing ethylene oxide with a hydrophobic base formed bythe addition of propylene oxide to the two hydroxyl groups of propyleneglycol. This hydrophobic portion of the molecule weighs from 1,000 to4,000. Ethylene oxide is then added to sandwich this hydrophobe betweenhydrophilic groups, controlled by length to constitute from about 10% byweight to about 80% by weight of the final molecule.

Tetronic® compounds are tetra-functional block copolymers derived fromthe sequential addition of propylene oxide and ethylene oxide toethylenediamine. The molecular weight of the propylene oxide hydrotyperanges from 500 to 7,000; and, the hydrophile, ethylene oxide, is addedto constitute from 10% by weight to 80% by weight of the molecule.

2. Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from 8 to 18 carbon atoms with from3 to 50 moles of ethylene oxide. The alkyl group can, for example, berepresented by diisobutylene, di-amyl, polymerized propylene, iso-octyl,nonyl, and di-nonyl. These surfactants can be polyethylene,polypropylene, and polybutylene oxide condensates of alkyl phenols.Examples of commercial compounds of this chemistry are available on themarket under the trade names Igepal® manufactured by Rhone-Poulenc andTriton® manufactured by Union Carbide.

3. Condensation products of one mole of a saturated or unsaturated,straight or branched chain, generally aliphatic alcohol having from 6 to24 carbon atoms with from 3 to 50, preferably from 3 to 18 moles ofethylene oxide. The alcohol moiety can consist of mixtures of alcoholsin the above delineated carbon range or it can consist of an alcoholhaving a specific number of carbon atoms within this range. Preferredalcohols for use in the composition of the present invention have alkylmoieties like decyl, dodecyl, tridecyl, tetradecyl, pentadecyl orhexadecyl or mixtures thereof. Examples of like commercial surfactantare available under the trade names Neodol® manufactured by ShellChemical Co. Alfonic® manufactured by Vista Chemical Co., Tegotens®manufactured by Goldschmidt, Genapol® manufactured by Clariant andLutensol® manufactured by BASF.

The ethoxylated C₆-C₂₄ fatty alcohols may additionally be propoxylated.Particularly those are suitable surfactants for use in the presentcompositions that are water soluble. Suitable ethoxylated andpropoxylated fatty alcohols include the C₆-C₂₄, preferably the C₁₀-C₁₈ethoxylated and propoxylated fatty alcohols with a degree ofethoxylation of from 3 to 50, preferably of from 3 to 18, and with adegree of propoxylation of from 3 to 50, preferably of from 3 to 18 andmore preferred of from 4 to 10. Such surfactants are commerciallyavailable, for example under the trade names Genapol® manufactured byClariant.

4. Condensation products of one mole of saturated or unsaturated,straight or branched chain carboxylic acid having from 8 to 18 carbonatoms with from 6 to 50 moles of ethylene oxide. The acid moiety canconsist of mixtures of acids in the above defined carbon atoms range orit can consist of an acid having a specific number of carbon atomswithin the range. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Nopalcol® manufactured byHenkel Corporation and Lipopeg® manufactured by Lipo Chemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention. All ofthese ester moieties have one or more reactive hydrogen sites on theirmolecule which can undergo further acylation or ethylene oxide(alkoxide) addition to control the hydrophilicity of these substances.Care must be exercised when adding these fatty ester or acylatedcarbohydrates to compositions of the present invention containingamylase and/or lipase enzymes because of potential incompatibility.

Examples of nonionic low foaming surfactants include:

5. Compounds from (1) which are modified, essentially reversed, byadding ethylene oxide to ethylene glycol to provide a hydrophile ofdesignated molecular weight; and, then adding propylene oxide to obtainhydrophobic blocks on the outside (ends) of the molecule. Thehydrophobic portion of the molecule weighs from 1,000 to 3,100 with thecentral hydrophile including 10% by weight to 80% by weight of the finalmolecule. These reverse Pluronics® are manufactured by BASF Corporationunder the trade name Pluronic® R surfactants.

Likewise, the Tetronic® R surfactants are produced by BASF Corporationby the sequential addition of ethylene oxide and propylene oxide toethylenediamine. The hydrophobic portion of the molecule weighs from2,100 to 6,700 with the central hydrophile including 10% by weight to80% by weight of the final molecule.

6. Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmultifunctional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to 5 carbon atoms; and mixtures thereof. Suchsurfactants are commercially available, for example under the tradenames Tegotens® manufactured by Goldschmidt and Dehypon® manufactured byCognis. Also included are reactants such as thionyl chloride whichconvert terminal hydroxy groups to a chloride group. Such modificationsto the terminal hydroxy group may lead to all-block, block-heteric,heteric-block or all-heteric nonionics.

Additional examples of effective low foaming nonionics include:

7. The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkylene oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n)(C₂H₄O)_(m)H wherein Y is the residue of an organiccompound having from 1 to 6 carbon atoms and one reactive hydrogen atom,n has an average value of at least 6.4, as determined by hydroxyl numberand m has a value such that the oxyethylene portion constitutes 10% to90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least 2, n has a value suchthat the molecular weight of the polyoxypropylene hydrophobic base is atleast 900 and m has value such that the oxyethylene content of themolecule is from 10% to 90% by weight. Compounds falling within thescope of the definition for Y include, for example, propylene glycol,glycerol, pentaerythritol, trimethylolpropane, ethylenediamine and thelike. The oxypropylene chains optionally, but advantageously, containsmall amounts of ethylene oxide and the oxyethylene chains alsooptionally, but advantageously, contain small amounts of propyleneoxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from 8 to 18 carbon atoms and containing xreactive hydrogen atoms in which x has a value of 1 or 2, n has a valuesuch that the molecular weight of the polyoxyethylene portion is atleast 44 and m has a value such that the oxypropylene content of themolecule is from 10% to 90% by weight. In either case the oxypropylenechains may contain optionally, but advantageously, small amounts ofethylene oxide and the oxyethylene chains may contain also optionally,but advantageously, small amounts of propylene oxide.

8. Polyhydroxy fatty acid amide surfactants suitable for use in thepre-sent compositions include those having the structural formulaR²CONR¹Z in which: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R² is aC₅-C₃₁ hydrocarbyl, which can be straight-chain; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z can be derived froma reducing sugar in a reductive amination reaction; such as a glycitylmoiety.

9. Suitable nonionic alkylpolysaccharide surfactants, particularly foruse in the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from 6 to 30, preferably from 8 to 12carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilicgroup containing from 1.3 to 10 saccharide units. Any reducingsaccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,galactose and galactosyl moieties can be substituted for the glucosylmoieties. (Optionally the hydrophobic group is attached at the 2-, 3-,4-, etc. positions thus giving a glucose or galactose as opposed to aglucoside or galactoside.) The intersaccharide bonds can be, e.g.,between the one position of the additional saccharide units and the 2-,3-, 4-, and/or 6-positions on the preceding saccharide units.

10. Fatty acid amide surfactants suitable for use in the presentcompositions include those having the formula: R⁶CON(R⁷)₂ in which R⁶ isan alkyl group containing from 7 to 21 carbon atoms and each R⁷ isindependently hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

11. A useful class of non-ionic surfactants includes the class definedas alkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(s)N-(EO)_(t)H,R²⁰—(PO)_(s)N-(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H;in which R²⁰ is an alkyl, alkenyl or other aliphatic group, or analkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EOis oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations onthe scope of these compounds may be represented by the alternativeformula:R²⁰—(PO)_(v)—N[(EO)_(w)H][(EO)_(z)H]in which R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.

These compounds are represented commercially by a line of products soldby Huntsman Chemicals as nonionic surfactants. A preferred chemical ofthis class includes Surfonic™ PEA 25 Amine Alkoxylate.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and Detergents”(Vol. I and II by Schwartz, Perry and Berch).

Also useful in the present invention are surface active substances whichare categorized as anionics because the charge on the hydrophobe isnegative; or surfactants in which the hydrophobic section of themolecule carries no charge unless the pH is elevated to neutrality orabove (e.g. carboxylic acids). Carboxylate, sulfonate, sulfate andphosphate are the polar (hydrophilic) solubilizing groups found inanionic surfactants. Of the cations (counter ions) associated with thesepolar groups, sodium, lithium and potassium impart water solubility;ammonium and substituted ammonium ions provide both water and oilsolubility; and, calcium, barium, and magnesium promote oil solubility.

As those skilled in the art understand, anionics are excellent detersivesurfactants and are therefore favored additions to heavy duty detergentcompositions. Generally, however, anionics have high foam profiles.Anionics are very useful additives to preferred compositions of thepresent invention. Further, anionic surface active compounds are usefulto impart special chemical or physical properties other than detergencywithin the composition. Anionics can be employed as gelling agents or aspart of a gelling or thickening system. Anionics are excellentsolubilizers and can be used for hydrotropic effect and cloud pointcontrol.

The majority of large volume commercial anionic surfactants can besubdivided into five major chemical classes and additional sub-groupsknown to those of skill in the art and described in “SurfactantEncyclopedia,” Cosmetics & Toiletries, Vol. 104 (2) 71-86 (1989). Thefirst class includes acylamino acids (and salts), such asacylglutamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates),taurates (e.g. N-acyl taurates and fatty acid amides of methyl tauride),and the like. The second class includes carboxylic acids (and salts),such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g.alkyl succinates), ether carboxylic acids, and the like. The third classincludes phosphoric acid esters and their salts. The fourth classincludes sulfonic acids (and salts), such as isethionates (e.g. acylisethionates), alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates(e.g. monoesters and diesters of sulfosuccinate), and the like. Thefifth class includes sulfuric acid esters (and salts), such as alkylether sulfates, alkyl sulfates, and the like.

Appropriate anionic surfactants represent sulfosuccinates represented bythe general formula:

with R¹=C₈₋₁₂, R²=H, C₈₋₁₂, and X=Na, K, NH₄ ⁺. The alkyl residue of theester moiety may be linear or branched, preferably it is linear. It isparticularly preferred to use sulfosuccinate compounds which are watersoluble. A suitable example represents sodiumdiisooctyl sulfosuccinate.

Anionic sulfate surfactants suitable for use in the present compositionsinclude the linear and branched primary and secondary alkyl sulfates,alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenolethylene oxide ether sulfates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and—N—(C₁-C₂ hydroxyalkyl) glucamine sulfates, and sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described herein).

Examples of suitable synthetic, water soluble anionic detergentcompounds include the ammonium and substituted ammonium (such as mono-,di- and triethanolamine) and alkali metal (such as sodium, lithium andpotassium) salts of the alkyl mononuclear aromatic sulfonates such asthe alkyl benzene sulfonates containing from 5 to 18 carbon atoms in thealkyl group in a straight or branched chain, e.g., the salts of alkylbenzene sulfonates or of alkyl toluene, xylene, cumene and phenolsulfonates; alkyl naphthalene sulfonates, diamyl naphthalene sulfonates,and dinonyl naphthalene sulfonates and alkoxylated derivatives.

Anionic carboxylate surfactants suitable for use in the presentcompositions include the alkyl ethoxy carboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps (e.g. alkyl carboxyls).Secondary soap surfactants (e.g. alkyl carboxyl surfactants) useful inthe present compositions include those which contain a carboxyl unitconnected to a secondary carbon. The secondary carbon can be in a ringstructure, e.g. as in p-octyl benzoic acid, or as in alkyl-substitutedcyclohexyl carboxylates. The secondary soap surfactants typicallycontain no ether linkages, no ester linkages and no hydroxyl groups.Further, they typically lack nitrogen atoms in the head-group(amphiphilic portion). Suitable secondary soap surfactants typicallycontain 11-13 total carbon atoms, although more carbons atoms (e.g., upto 16) can be present.

Other anionic detergents suitable for use in the present compositionsinclude olefin sulfonates, such as long chain alkene sulfonates, longchain hydroxyalkane sulfonates or mixtures of alkenesulfonates andhydroxyalkane-sulfonates. Also included are the alkyl sulfates, alkylpoly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy) sulfatessuch as the sulfates or condensation products of ethylene oxide andnonyl phenol (usually having 1 to 6 oxyethylene groups per molecule).Resin acids and hydrogenated resin acids are also suitable, such asrosin, hydrogenated rosin, and resin acids and hydrogenated resin acidspresent in or derived from tallow oil.

In particular in case an additional disinfective effect is desired itmay be advantageous to use one or more cationic surfactants. Suitablecationic surfactants represent quaternary ammonium compounds. They canbe exemplified by short-chain, water-soluble quaternary ammoniumcompounds like trihydroxyethyl methyl ammonium methosulfate, alkyldimethyl ammonium adipates or alkyl trimethyl ammonium chlorides,dialkyl dimethyl ammonium chlorides and trialkyl methyl ammoniumchlorides, for example cetyl trimethyl ammonium chloride, stearyltrimethyl ammonium chloride, distearyl dimethyl ammonium chloride,lauryl trimethyl ammonium chloride, lauryl dimethyl benzyl ammoniumchloride and tricetyl methyl ammonium chloride. Moreover, benzalkoniumsalts, benzethonium salts and biguanide compounds may be used in thepresent composition.

Further suitable cationic surfactants correspond to formulae (IX) and(X):

where R and R¹ represent an acyclic alkyl group having 12 to 24 carbonatoms, R² is a saturated C₁₋₄ alkyl or hydroxyalkyl group, R³ is eitherthe same as R, R¹ or R² or represents an aromatic radical. X⁻ is eithera halide, a methosulfate, a methophosphate or a phosphate ion or amixture thereof. Examples of cationic compounds corresponding to formula(IX) represent didecyl dimethyl ammonium chloride, ditallow dimethylammonium chloride or dihexadecyl ammonium chloride.

Compounds corresponding to formula (X) are so-called esterquats.Esterquats are distinguished by excellent biodegradability. In thatformula R⁴ is an aliphatic acyl group containing 12 to 22 carbon atomsand 0, 1, 2 or 3 double bonds, R⁵ is H, OH or O(CO)R⁶, R⁷ independentlyof R⁶ stands for H, OH or O(CO)R⁸, R⁷ and R⁸ independently of oneanother representing an aliphatic acyl group containing 12 to 22 carbonatoms and 0, 1, 2 or 3 double bonds. m, n and p independently of oneanother can have a value of 1, 2 or 3. X⁻ can be a halide, amethosulfate, a methophosphate or a phosphate ion or a mixture thereof.Preferred compounds contain the group O(CO)R⁷ for R⁴ and C₁₆₋₁₈ alkylgroups for R⁴ and R⁷. Particularly preferred compounds are those inwhich R¹ is also OH. Examples of compounds corresponding to formula (X)are methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyloxyethyl)-ammoniummethosulfate, bis-(palmitoyl)-ethyl hydroxyethyl methyl ammoniummethosulfate ormethyl-N,N-bis-(acyloxyethyl)-N-(2-hydroxyethyl)-ammonium methosulfate.Commercially available examples for quaternized compounds correspondingto formula (X) represent methyl hydroxyalkyl dialkoyloxyalkyl ammoniummethosulfates marketed by Stepan under the name of Stepantex® or theCognis products known under the name of Dehyquart® as well as theGoldschmidt-Witco products known under the name of Rewoquat®. Otherpreferred compounds are the diesterquats corresponding to formula (XI)which are obtainable under the name of Rewoquat® W 222 LM or CR 3099.

In formula (XI), R⁹ and R¹⁰ independently of one another each representan aliphatic acyl group containing 12 to 22 carbon atoms and 0, 1, 2 or3 double bonds.

Besides the quaternary compounds described above, other known compoundsmay also be used, including for example quaternary imidazoliniumcompounds corresponding to formula (XII):

in which R¹³ represents H or a saturated alkyl group containing 1 to 4carbon atoms, R¹¹ and R¹² independently of one another represent analiphatic, saturated or unsaturated alkyl group containing 12 to 18carbon atoms, R¹¹ alternatively may also represent O(CO)R¹⁴, R¹⁴ beingan aliphatic, saturated or unsaturated alkyl group containing 12 to 18carbon atoms, and Z is an NH group or oxygen and X⁻ is an anion asspecified above. q may be an integer of 1 to 4.

Other suitable quaternary compounds correspond to formula (XIII):

where R¹⁵, R¹⁶ and R¹⁷ independently of one another represent a C₁₋₄alkyl, alkenyl or hydroxyalkyl group, R¹⁸ and R¹⁹ independently of oneanother represent a C₈₋₂₈ alkyl group and r is a number of 1 to 5.

Other suitable compounds correspond to the following formula:

and may be alkylamidoamines in their non-quaternized form or, asillustrated, in their quaternized form. In formula (XIV), R²⁰ may be analiphatic acyl group containing 12 to 22 carbon atoms and 0, 1, 2 or 3double bonds. s may assume a value of 0 to 5. R²¹ and R²² independentlyof one another represent H, C₁₋₄ alkyl or hydroxyalkyl. Preferredcompounds are fatty acid amidoamines, such as stearylamidopropyldimethylamine obtainable under the name of Tego Amid® S 18 or the3-tallowamidopropyl trimethylammonium methosulfate obtainable asStepantex® X 9124, which are distinguished by ready biodegradability.

Examples of amphoteric or zwitterionic surfactants, respectively, whichare suitable in the composition according to the present invention,include alkyl carboxybetaines, alkyl sulfobetaines, alkylhydroxysulfobetaines, alkyl amidobetaines, imidazolinium betaines, alkyldiaminoethyl glycines, dialkyl diaminoethyl glycines or a mixturethereof.

Anyway, in case a mixture of surfactants of one or more types is usedthe surfactants should be chosen such that they rapidly wet the surfaceand show an acceptable residue performance i.e. they do not tend toleave reams, stripes or spots on the surface after the surface hasdried. It is also preferred that the one or more surfactants are chosensuch that a more or less clear solution results.

In a preferred embodiment, in case the pH value of the composition isequal to or above 7 it is preferred to use a mixture of anionic andnonionic surfactants.

In an especially preferred embodiment such a combination of surfactantscomprises either at least two nonionics or one or two nonionics incombination with at least one anionic, preferably with two or moreanionics. A particular advantageous composition includes at least oneamine oxide, and two to four, preferably two anionics, especiallyincluding at least one C₁₀-C₁₆ alkylsulfonate and at least onesodiumdialkyl sulfosuccinate like sodium diisooctyl sulfosuccinate. Suchcompositions are commercially available like the one designated asRewopol® WP35, manufactured by Goldschmidt/Degussa.

The best results are achieved if the surfactants are comprised in thecomposition in a total amount of from 0 to 5 wt. %, preferably 0.01 to 3wt. %, more preferred of from 0.1 to 1.5 wt. %, still more preferred offrom 0.3 to 0.7 wt. % and most preferred of from 0.5 to 0.6 wt. % basedon the total end use composition. Those amounts refer to the amounts ofthe active substance. In case commercially available products areemployed which are diluted for example with water this has to be takeninto account. Moreover the amounts refer to the end use composition.This especially should be born in mind in case a concentrate is preparedand not the use solution directly.

As to the concentrate the surfactants preferably are contained thereinin a total amount of from 0.05 to 15 wt. %, preferably of from 0.5 to 10wt. % and more preferred of from 1.2 to 6 wt. %.

As already mentioned before, the composition of the present inventionmay be prepared in the form of a concentrate or in the form of an enduse composition. The concentrate should comprise an amount of watercorresponding to 10 to 30 wt. %, preferably 15 to 25 wt. % and morepreferred 18 to 22 wt. % of the water as contained in the total end usecomposition whereas the water content in the end use compositionpreferably ranges from 70 to 99.97 wt. %, preferably of from 80 to 99wt. % and more preferred of from 85 to 98 wt. % based on the totalcomposition.

The water content in the concentrate as mentioned above preferablycorresponds to 10 to 90 wt. %, more preferred to 20 to 70 wt. % and mostpreferred to 35 to 55 wt. % based on the concentrate composition.

The composition according to the present invention may additionallycontain one or more further compounds which are usually used incompositions for cleaning or treating a surface, in particular a hardsurface. Such additives can be exemplified by organic solvents, agentsfor adjusting the pH value, buffering agents, complexing agents,perfumes, coloring agents, builders, disinfecting agents, enzymes,bleaching agents, finishing agents and preservatives.

The compositions according to the present invention may be adjusted suchthat they have a pH value of from 1 to 12. Alkaline compositionsaccording to the pre-sent invention preferably have a pH value of from 8to 10 whereas acidic compositions preferably have a pH value of from 2to 5. Depending on whether the composition is alkaline or acidic theadditives and to some extent even the main components in the componentsslightly differ. For example as mentioned above, in an acidiccomposition it is particularly preferred to use one or more nonionicswhereas in an alkaline composition it is most preferred to use a mixtureof one or more anionics and one or more nonionics.

Moreover, as bases typically are added in alkaline compositions toachieve a corresponding high pH value this is not necessary and also notdesired with acidic compositions.

Moreover, the kind of the additives used and their amounts should bechosen such that a clear solution results.

The one or more organic solvents are intended to provide a compositionwith good wetting properties and to facilitate the evaporation of thecomposition on the surface to be cleaned or treated to achieve a rapiddrying. Suitable organic solvents for use in the present compositionrepresent alkylene glycol (mono and/or di) alkyl ether like ethyleneglycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonobutyl ether, propylene glycol monophenyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, dipropylene glycol monomethyl ether, dipropyleneglycolmonoethyl ether, dipropylene glycol monobutal ether, triethyleneglycol monobutyl ether, tripropylene glycol dimethyl ether, and mixturesthereof. Propylene glycol monobutyl ether is most preferred.

Moreover aliphatic monohydric, dihydric or trihydric alcohols having 1to 4 carbon atoms may function as organic solvent in the presentcomposition as well. Suitable alcohols represent methanol, ethanol,n-propanol, iso-propanol, n-butanol, isobutanol, sec-butanol, tert.butanol, glycerol, ethylene glycol, propylene glycol or mixturesthereof.

Preferably the one or more organic solvents are contained in thecomposition in a total amount of from 0 to 10 wt. % more preferred offrom 1 to 8 wt. %, most preferred of from 2 to 5 wt. % based on thewhole end use composition. Those amounts refer to the amount of theactive substance. In case commercially available products are employedwhich are diluted for example with water this has to be taken intoaccount. Moreover the amounts refer to the end use composition. Thisespecially should be born in mind in case a concentrate is prepared andnot the use solution directly.

As to the concentrate the one or more organic solvents preferably arecontained therein in a total amount of from 0 to 25 wt. %, preferably offrom 1 to 20 wt. % and more preferred of from 5 to 15 wt. %.

For adjusting the desired pH value depending on the pH of the mixturecomprising the three main components, organic or inorganic acids orbases may be used. They may also include buffering substances. Suitablebases for use in the present compositions represent ammonia, preferablyin form of its aqueous solution, alkylamines having 1 to 8 carbon atomsin the alkyl moiety like monoethanolamine and diethanolamine. Furtheralkaline compounds for use in the present composition are exemplified byalkali hydroxides, like sodium hydroxide or potassium hydroxide.

Preferably the one or more alkaline substances are containedsubstantially in the alkaline composition in a total amount of from 0 to5 wt. % more preferred of from 0.01 to 3 wt. %, most preferred of from0.05 to 1.5 wt. % based on the whole end use composition. Those amountsrefer to the amount of the active substance. In case commerciallyavailable products are employed which are diluted for example with waterthis has to be taken into account. It is preferred that no alkalinecompounds are used to form the acidic compositions.

As to the concentrate the one or more alkaline substances preferably arecontained therein in a total amount of from 0 to 10 wt. %, preferably offrom 0.05 to 5 wt. % and more preferred of from 0.1 to 2 wt. %.

Examples of appropriate acids for use in the present compositionsinclude organic acids like acetic acid, citric acid, glycolic acid,lactic acid, succinic acid, adipic acid, malic acid, tartaric acid andgluconic acid and also amidosulfuric acid. Besides, mineral acids likehydrochloric acid, sulfuric acid and nitric acid can be employed.Mixtures of any of those acids may also be used. The acids may be usedmainly for acidic compositions but may also be included in the alkalinecompositions to adjust a specific pH value.

Whereas alkaline compounds preferably are only used to form alkalinecompositions acids may be used for the preparation of acidic as well asalkaline compositions. In alkaline compositions acidic compoundstypically function as regulators of the pH value. Consequently,concerning the amount of acidic components it should be distinguishedbetween acidic and alkaline compositions. Preferably the one or moreacids are contained in an alkaline composition in a total amount of from0 to 5 wt. % more preferred of from 0.01 to 3 wt. %, most preferred offrom 0.02 to 1.5 wt. % based on the whole end use composition. As toacidic compositions, the one or more acids should be contained thereinin a total amount of from 0 to 25 wt. % more preferred of from 0.1 to 15wt. %, most preferred of from 0.5 to 5 wt. % based on the whole end usecomposition. Those amounts refer to the amount of the active substance.In case commercially available products are employed which are dilutedfor example with water this has to be taken into account.

As to the alkaline concentrates the one or more acids preferably arecontained therein in a total amount of from 0 to 10 wt. %, preferably offrom 0.05 to 5 wt. % and more preferred of from 0.1 to 2 wt. %.Analogous, the acidic concentrates preferably contain the one or moreacids in a total amount of from 0 to 50 wt. %, preferably of from 0.5 to25 wt. % and more preferred of from 2 to 10 wt. %.

Furthermore the composition according to the present invention maycomprise complexing agents. Suitable compounds for use in the presentcomposition include ethylenediaamine tetraacetic acid, nitrilotriaceticacid, phosphates, polyhydroxy carboxylic acids, citrates, triethanolamine, sodiummethylglycin diacetate, which is especially preferred, andmixtures thereof.

Preferably the one or more complexing agents are contained in thecomposition in a total amount of from 0 to 5 wt. % more preferred offrom 0.01 to 3 wt. %, most preferred of from 0.02 to 1.5 wt. % based onthe whole end use composition. Those amounts refer to the amount of theactive substance. In case commercially available products are employedwhich are diluted for example with water this has to be taken intoaccount.

As to the concentrate the one or more complexing agents preferably arecontained therein in a total amount of from 0.05 to 15 wt. %, preferablyof from 0.5 to 10 wt. % and more preferred of from 1.2 to 6 wt. %.

Although the sequence for admixing the single components is notparticularly limited, in order to obtain a stable and clear solution thealkaline composition is pre-pared by mixing a minimum amount of waterwhich corresponds to 10 to 30 wt. %, preferably 15 to 25 wt. % and morepreferred 18 to 22 wt. % of the water as contained in the total end usecomposition with the combined surfactants and organic solvents, ifpresent. Afterwards the amphoteric, organic polynitrogen-compounds areadded followed by the addition of the nanoparticles. The furtheradditives like bases, perfumes, coloring agents, complexing agents areincorporated. The desired amount of acid may be added here or at theend, but preferably not at the end. After having mixed the abovementioned compounds a concentrate is obtained. The concentrate may befurther diluted with the remaining amount of water to obtain the end usecomposition or it may be sold as such and the remaining amount may beadded by the user.

When preparing an acidic composition it is preferred to first dose thetotal amount of water supposed to be contained in the concentrate or theend use solution, depending on the desired composition. Afterwards theother components are added wherein the surfactants, if contained,preferably are added before admixing any perfume. When having prepared aconcentrate it may directly or later on be diluted to obtain the end usecomposition.

Surprisingly, it has been found out that the composition as specifiedabove shows an improved performance like improved drying performance, areduced re-soiling and facilitated re-cleaning properties with an atleast not deteriorated overall cleaning performance in comparison withthe compounds of the state of the art. It was particularly surprisingthat the combination of the main components, amphoteric, organicpolynitrogen-compounds having at least 3 nitrogen atoms contained in themolecule in the form of an amine and/or amide, surfactants and inorganicnanoparticles, results in stable compositions. As nanoparticlesspecified herein typically exhibit a reduced stability under acidicconditions and the organic polynitrogen compounds show an reducedstability or at least a reduced performance in alkaline solution, itcould not have been expected that said combination of components wouldresult in a stable composition under alkaline as well as under acidicconditions and as well shows improved properties.

A further object of the present invention relates to a method fortreating and/or cleaning a surface comprising

-   -   a) applying the composition as specified above onto said surface    -   b) rinsing, drying, blowing, sucking off, heating and/or wiping        the surface.

Preferably, the compositions are used for cleaning surfaces and inparticular hard surface, more preferred polar surfaces. Suitablesurfaces to be cleaned using the composition according to the presentinvention include glass, like windows, but also mirrors, lenses, forexample of optical devices, spectacles or glasses used for drinking. Thecomposition may also be used for cleaning other surfaces which are moreor less frequently rinsed with contaminated or clean water like showers,bathtubs and floors, walls or windows in a bathroom, in a kitchen(either private or in a canteen kitchen), in public baths or saunas, ingymnasiums or other sport facilities. Further surfaces which may becleaned with the present composition represent dishware in a dishwasher.However, in the dishwasher the compositions is preferably used as arinse aid. It is also advantageous to use the present composition onsurfaces of automobiles like windows but also lacquered surfaces of thecar body. Metal surfaces and other lacquered surface may also be cleanedwith the present composition. Amazingly the present composition is alsoappropriate for textile surfaces which are hydrophilized by treatmentwith the present composition.

The composition of the present invention may be applied by any meansknown by the skilled person, including spraying, pouring, wiping,dipping, misting, rolling, brushing and foaming. Although it is alsopossible to apply the composition in the form of its concentrate thebest performance is obtained when applying the diluted concentrate asend use composition.

After having applied the composition the surface may be rinsed, althoughthis is not preferred. The surface should rather be allowed to air-dryor it should at least partly be dried with a cloth or other kinds oftextiles or cellulose fabrics.

The composition according to the present invention is particularly usedto reduce the resoiling of the surface, to improve the soil releaseproperties and/or to generally hydrophilize the surface.

To avoid a permanent change of the surface to be cleaned or treated thecomposition according to the present invention is preferably notpermanent. This may be achieved by using watersoluble orwaterdispersible compounds as amphoteric organic polynitrogen compounds,like the ones specified above. Although the polynitrogen compounds maynot be removed from the surface with the next rinsing for example withwater, at least after several rinsing courses the components remainingon the surface, mainly the amphoteric organic polynitrogen compounds andthe nanoparticles, are removed. However, it can be desired to obtain anartificial permanent effect by repeating the application of thecomposition according to the present invention regularly. Thereby, aneven improved performance can be observed. However, even after repeatedtreatments the remains on the surface may easily be removed if desired.

The present invention will be further elucidated in the followingexamples. Unless otherwise indicated the amounts represent wt. %.

EXAMPLES

Table 1 shows some alkaline compositions which may be used in thepresent invention (Ex.) and also two comparative compositions (CEx.).

TABLE 1 CEx. CEx. Ex. Ex. Ex. Ex. Ex. 1 2 1 2 3 4 5 Water 93.28 93.5992.58 93.08 93.67 93.08 92.88 demineralized Isopropanol 3.0 3.0 3.0 — —3.0 3.0 Ethanol, — — — 3.0 3.0 — — 96% Propyl glycol 1.5 1.5 1.5 1.5 1.51.5 1.5 monobutyl ether Acetic acid, 0.34 0.03 0.04 0.04 0.03 0.04 0.0460% Citric acid × — — 0.5 — — — — 1 H₂O Ammonia, 25% 0.3 0.3 0.3 0.3 0.30.3 0.3 Surfactant, 0.5 0.5 0.5 0.5 0.5 0.5 0.5 65%¹⁾ Amphoteric — 0.50.5 0.5 0.5 0.5 0.5 polyamine²⁾ Colloidal silica 0.5 — 0.5 0.5 0.5 0.50.7 sol nanoparticles³⁾ Sodium methyl- 0.5 0.5 0.5 0.5 — 0.5 0.5 glycindiacetate (40%, aqueous solution) Perfume 0.08 0.08 0.08 0.08 0.08 0.080.08 pH value 9.9 9.9 10 9.9 9.9 9.9 9.8 ¹⁾mixture of anionic andnonionic surfactants containing decyldimethylaminoxide, sodium monoC₁₀-C₁₆ alkylester sulfonate, sodium diisooctyl sulfosuccinate in theform of an aqueous solution ²⁾obtained from polyethylenimine andpolyacrylic acid, 40% aqueous solution, supplied by BASF ³⁾aqueoussilica sol with a silica content of 30%, a BET surface area of 360 m²/g,and an average particle size of 7-9 nm

The compositions were prepared by pouring about 20% of the total amountof water into a container, adding a mixture of the surfactant and thesolvent thereto, followed by subsequent addition of the Sokalan® HP70,the colloidal silica sol, a mixture of perfume and ammonia, thecomplexing agent (sodium methylglycin diacetate) and the remainingamount of water. While adding the single compounds the mixture isstirred. Stirring is continued until a clear solution is obtained. Inorder to optimize the comparability of the single compositions the pHvalue is adjusted to about 9-10 by adding the required amount of aceticacid.

Pre-testing of the single compositions showed that the best performancewas obtained with examples 1 and 4. Therefore, the single performancetests were carried out using the composition of examples 1 and 4 incomparison with the compositions of comparative example 1 and 2.

Hydrophilizing Effect

Each of the compositions was sprayed onto the surface of one ofidentical plates made of glass in an amount of about 7-14 g/m². Thesurface was dried by wiping it with a cellulose fabric. Afterwards thetest surfaces were sprayed with tap water and the wetted surface wasallowed to dry. The spray behavior, the behavior of the flowing off thesurface as well as the residues after drying were determined visually.The results are shown in table 2.

TABLE 2 Spraying Flow off Drying Appearance behavior behavior speedafter drying CEx. Easy to spread, No hydrophilicity, 15 min Lots of 1 noreams lots of drops droplike residues CEx. Easy to spread, Lowhydrophilicity, 15 min Lots of 2 no reams film rapidly tears droplikeopen residues Ex. Easy to spread, High hydrophilicity, 10 min In theupper 1 no reams uniform film part some reams, more reams in the lowerpart Ex. Easy to spread, High hydrophilicity, 10 min In the upper 4 noreams uniform film part some reams, more reams in the lower part

The results presented in table 2 show that a composition comprising anamphoteric polyamine as well as silica sol nanoparticles besidessurfactants imparts a markedly increased hydrophilicity to a glasssurface in comparison to a composition containing surfactants and eitheronly the amphoteric polyamine or only the silica sol nanoparticles.

In the following, different surfaces were tested with regard to thetendency to become hydrophilized by the various compositions. Theapplication of the single compositions onto the surface was carried outas described in the previous hydrophilicity test. The results are shownin table 3.

TABLE 3 Hyrophilization on CEx. 1 CEx. 2 Ex. 1 Ex. 4 Glass No Yes YesYes Stainless steel Yes No Yes Yes Marble* Yes Yes Yes Yes Tiles,glazed** Yes/No Yes/No Yes/No Yes/No Acrylic plastic Yes Yes Yes Yes*The untreated surface itself had such a high surface tension that therewas no difference concerning the various compositions. **Whereas theuntreated surface leads to formation of large, long drops and stripes,the treated surface leads to a formation of lots of small drops. Theperformance of each of the various compositions did not significantlydiffer.

The results presented in table 3 show that with regard to marble, whichas such has a hydrophilic surface without further treatment, tiles andacrylic plastic all compositions provide a similar hydrophilic effect tothe treated surface. However, as to the glass surface the hydrophilicityof the inventive compositions is increased in comparison to thecomposition which is free of any amphoteric polynitrogen compound. Incontrast thereto the hydrophilic effect of the inventive compositions isincreased on metal in comparison with the composition which is free ofany silica sol nanoparticles.

Cleaning Performance

To determine the cleaning performance of the compositions CEx. 1, CEx. 2and Ex. 4 a gardner test was carried out. In this test glass stripeswere soiled on a surface area of 3.9 cm×26 cm with a soiling called“window soiling, inside”, commercially available from theWäschereiforschung Krefeld (WFK), comprising skin fat, oil and pigmentsdiluted with ethyl acetate.

In order to create a more stubborn soiling the glass stripes werepre-treated with hard water. Water having a water hardness of 42.2° dHwas prepared by introducing 6 ml of a solution A into a volumetric 1000ml-flask and adding 600 ml demineralized water thereto. Afterwards 8 mlof Solution B were added and the flask was filled up with water to avolume of 1000 ml.

Solution A was prepared by dissolving 19.84 g anhydrous MgCl₂ and 46.24g anhydrous CaCl₂ in demineralized water and adding furtherdemineralized water to result in 1000 ml of an aqueous solution.Solution B was prepared by dissolving 35.02 g anhydrous NaHCO₃ indemineralized water and adding further demineralized water to result in1000 ml of an aqueous solution.

At first the glass stripes were pre-treated by rinsing withdemineralized water, cleaning with isopropanol and drying with acellulose fabric. Afterwards the water having a water hardness of 42.20dH obtained above was sprayed in an amount of 60 ml/m² on the glassstripes and the thus treated glass stripes were dried.

11.07 g of the soiling were regularly distributed onto the thuspre-treated glass surface. The soiled test stripes were placed and fixedin a gardner testing device (supplied by Erichsen GmbH, model 494). Thegardner test was carried out according to DIN ASTM-515. A sponge wassoaked with 6 ml of the single compositions (one in a run) and placed ina fixed carrier of the testing device. The device moved the soakedsponge 4 times from one end of the soiled surface to the other and backwith a speed of 0.4 m/s and a contact pressure of 8.2 N. After havingfinished the four cycles the test stripe is removed from the device andthe remaining soiling is quantified by means of reflection measurementusing a Chroma Meter CR 200, supplied by Minolta. The value obtainedrepresents the percentage of the cleaning performance based on a stripewhich was not soiled. Thus a completely cleaned stripe would obtain avalue of 100. As further comparative “composition” tap water is used tosoak the sponge. For each test stripe the reflection was measured onseven spots which were coincidentally chosen. The resulting values whichare shown in table 4 represent the average of the seven measurements foreach stripe treated with one of the compositions. The results are shownin table 5.

TABLE 5 Tap water CEx. 1 CEx. 2 Ex. 4 Maximum value 67.60 71.66 71.0071.45 Minimum value 54.58 69.38 70.37 70.34 Δ (max-min) 13.2 2.28 0.631.11 Stand. dev. 4.95 0.69 0.21 0.37 Average 60.20 70.76 70.63 70.92

The results in table 5 show that the compositions all show similarcleaning properties which are markedly better than the cleaningproperties of pure water. However, neither the silica sol nanoparticlesnor the amphiprotic polynitrogen compound seem to influence the cleaningproperties.

Facilitated Cleaning of a Treated Surface

In order to determine the influence of the compositions on the easinessof a cleaning process subsequent to a pre-treatment with thecompositions, glass plates having a size of 25 cm×25 cm were pre-treatedeach with one of the compositions of CEx. 1, CEx. 2 and Ex. 4. Thecompositions were sprayed onto the glass plates in an amount of 1-2 g.After having dried the surfaces with a cellulose fabric each of theplates was soiled on one hand by generating two strokes, one with a redand one with a black permanent marker (supplied by Edding) and on theother hand provided with a print of a hand creamed each time with anidentical amount of a hand cream (SILONDA® liquid, supplied by Ecolab).Afterwards each of the vertically placed plates was sprayed with about10 to 30 ml of tap water above the soiling such that the soiling onlygets into contact with the water when it runs down the surface and notduring the process of spraying the water onto the surface. Thereby, itcan be excluded that the soiling is removed from the surface onlybecause of the pressure of the water sprayed against the soiling.Afterwards the plates were allowed to air-dry. The cleaning performancewas evaluated visually.

TABLE 6 Tap water CEx. 1 CEx. 2 Ex. 4 Removal of None None Very littleRemoval in edding removal places Removal of Lots of drops, Hand printHand print Only little hand print complete hand almost partly residues(from print complete removed the fingertips)

As could be expected pre-treatment with water had no influence on thefacilitation of a cleaning process subsequent to the pre-treatment.However, the composition which is free of any amphoteric polynitrogencompound shows a low tendency to facilitate the cleaning in a cleaningprocess subsequent to a pre-treatment. In contrast thereto the presenceof amphoteric polyamine (in the inventive composition as well as in thecomposition of CEx. 2) results in a facilitation of the cleaning if thesurface was pre-treated with the corresponding compositions.

Surprisingly, the combination of an amphoteric polynitrogen compound andcolloidal silica sol nanoparticles shows an increased effect althoughthe composition of CEx. 1 which contains silica sol nanoparticles but isfree of amphoteric polyamine, shows almost no effect. It can be observedvery well that each amount of water running over the soiling seems towash away a part of the soiling without using any pressure or othercleaning means. The effect especially occurs with respect to the removalof the hand print but can also be observed in a minor extent with theedding strokes applied on the glass plates pre-treated with thecomposition according to the present invention.

The following table 7 shows some acidic compositions which may be usedin the present invention (Ex.) and also three comparative compositions(CEx.).

TABLE 7 CEx. 1 CEx. 2 CEx. 3 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Water demineralized98.47 97.97 97.97 97.45 96.97 97.45 96.97 Lactic acid 1.0 1.0 1.0 — —1.0 1.0 Citric acid × 1 H₂O — — — 1.0 1.0 — — Isotridecanol, 8 EO¹⁾ 0.50.5 0.5 0.5 — 0.5 — Isotridecanol, 10 EO²⁾ — — — — — — 1.0 Fatty alcoholethoxylate, 11 EO³⁾ — — — — 1.0 — — Amphoteric polyamine⁴⁾ — 0.5 — 0.50.5 0.5 0.5 Colloidal silica sol nanoparticles⁵⁾ — — 0.5 0.5 0.5 0.5 0.5Perfume 0.03 0.03 0.03 0.05 0.03 0.03 0.03 pH value 2.6 2.6 2.6 2.4 2.52.6 2.5 ¹⁾fatty alcohol having 13 carbon atoms, wherein each mole offatty alcohol is ethoxylated with 8 moles of ethylenoxide ²⁾fattyalcohol having 13 carbon atoms, wherein each mole of fatty alcohol isethoxylated with 10 moles of ethylenoxide ³⁾fatty alcohol having 10carbon atoms, wherein each mole of fatty alcohol is ethoxylated with 11moles of ethylenoxide and the fatty alcohol ethoxylate is end-cappedwith butyleneoxide ⁴⁾obtained from polyethylenimine and polyacrylicacid, 40% aqueous solution, supplied by BASF ⁵⁾aqueous silica sol with asilica content of 30%, a pH value of 10.5 and an average particle sizeof 7 nm, wherein the silica is organically modified. The product issupplied by Akzo Nobel/Eka Chemicals

The above compositions were prepared by adding the single componentsmentioned to the total amount of water and mixing until an substantiallyclear solution was obtained. The perfume was added at last. Pre-testingshowed that the best performance was obtained with the composition ofEx. 3. Therefore, the following tests were carried out using saidcomposition in comparison with the ones of the comparative examples.

Cleaning Performance

In order to determine the cleaning performance of the compositions CEx.1, CEx. 2, CEx. 3 and Ex. 3 a gardner test was carried out in a similarmanner as described above. However, with the acidic compositions PVCtest stripes were used instead of test stripes made of glass. Moreover,the pre-treatment was omitted and the soiling specified above wasapplied directly onto the stripes. As a further difference the gardnertesting device moved the sponge soaked with one of the compositions 10times from one end of the soiled surface to the other and back. Theother parameters are as specified above. The results of the gardner testare shown in table 8.

TABLE 8 Tap water CEx. 1 CEx. 2 CEx. 3 Ex. 3 Maximum value 36 55 57 5959 Minimum value 24 48 52 52 52 Δ (max-min) 12 8 5 7 7 Stand. dev. 4 2 22 2 Average 30 51 55 55 55

The results in table 8 show that the compositions all show similarcleaning properties which are markedly better than the cleaningproperties of pure water. However, the silica sol nanoparticle as wellas the amphiprotic polynitrogen compound seem to influence the cleaningproperties only very slightly.

Hydrophilizing Effect

In order to determine the hydrophilizing effect, each of thecompositions was sprayed in an amount of about 1-1.5 g onto the surfaceof one of identical ceramic tiles of 20 cm×25 cm size (supplied bySteuler, named Logo). The surface was dried by wiping it with acellulose fabric. Afterwards the test surfaces were sprayed with tapwater and the wetted surfaces were allowed to dry completely. The spraybehavior, the behavior of the flowing off the surface (both resulting inthe application behavior) as well as the residues after drying(resulting in the behavior of the residue) were determined visually.While evaluating the behavior of the residue the occurrence of reams andbandings was taken into account. To facilitate the visual evaluation thetap water was colored blue. The test was independently carried out andthe results independently estimated by five persons for eachcomposition. The results are shown in table 9.

TABLE 9 Application Behavior Behavior of the Residue very very very veryEvaluation good good medium bad bad good good medium bad bad CEx. 1 x xCEx. 2 x x CEx. 3 x x Ex. 3 x x

The results in table 9 show that all acidic compositions which do notcomprise a combination of at least one type of nanoparticles and atleast one amphoteric polynitrogen compound show an deterioratedapplication behavior and result in more reams and bandings in comparisonwith the composition according to the present invention which comprisesboth components.

Ability to Dissolve Lime

As acidic cleaners typically are applied to remove lime residues forexample occurring in the kitchen, the bath room or any other damplocation, the compositions' abilities to dissolve lime were tested.Marble blocks having a size of 30 mm×30 mm×20 mm were brushed whilerinsing them with demineralized water. Afterwards the marble blocks wererinsed with ethanol to remove any fatty residues. The marble blocks weredried overnight in a drying oven at a temperature of 90° C. and weighedto result in weight m1. To determine the compositions' ability todissolve lime the weighed marble blocks were immersed into 200 ml of thecomposition to be tested and remained there for one hour at roomtemperature.

Afterwards the marble blocks again were brushed while rinsing them withdemineralized water, afterwards rinsed with ethanol, then driedovernight in a drying oven at a temperature of 90° C. and weighed toresult in weight m2. The ability mg to dissolve lime in the form of thepercentage reduction of the original weight of the marble blocks isobtained using the following equation:

${m\; g} = {\frac{{m\; 1} - {m\; 2}}{m\; 1} \times 100}$

For each composition three marble blocks were used and the average ofthe three obtained values of mg was determined. The resulting averagesare shown in table 10.

TABLE 10 Average mg CEx. 1 0.3110 CEx. 2 0.3180 CEx. 3 0.3310 Ex. 30.3692

Surprisingly, it has been found that the composition according to thepresent invention shows an increased ability to dissolve lime incomparison with the compositions which do not contain any nanoparticles,amphoteric polynitrogen compounds or both.

1. An aqueous composition comprising an amphoteric, organic amine oramide having at least 3 nitrogen atoms and formed by reactingpolyethylenimine and polyacrylic acid; and an inorganic nanoparticleselected from the group consisting of amorphous silicon dioxide, silicasols, fumed silica, and mixtures thereof, and sodiummethylglycinediacetate; wherein the organic amine or amide and the inorganicnanoparticle are present in a 1:1 weight ratio and wherein thecomposition forms a removable coating when applied to a surface.
 2. Thecomposition of claim 1, wherein the silica sola contain colloidal silicaparticles which are silanized, alumina-modified, or coated with aluminumoxide.
 3. The composition of claim 1, wherein the nanoparticle has anaverage particle size of from 1 to 50 nm.
 4. The composition of claim 1wherein the amine or amide is a polymer.
 5. The composition of claim 1further comprising a surfactant selected from the group consisting ofnonionic, anionic, cationic, amphoteric, zwitterionic and mixturesthereof.
 6. The composition of claim 5, wherein the surfactant isselected from the group consisting of anionic surfactants, nonionicsurfactants and mixtures thereof.
 7. The composition of claim 5, whereinthe composition does not contain any anionic surfactants if the pH valueof the composition is below
 7. 8. The composition of claim 1 wherein thenanoparticle is present in an amount from 0.01 to 3 wt. %.
 9. Thecomposition of claim 1 wherein the amine or amide is present in anamount from 0.01 to 3 wt. %.
 10. The composition of claim 5, wherein thesurfactant is present in an amount from 0.01 to 3 wt. %.
 11. Thecomposition of claim 1, further comprising from 70 to 99.97 wt. % water.12. The composition of claim 1, further comprising a compound selectedfrom the group consisting of organic solvents, agents for adjusting thepH value, buffers, perfumes, coloring agents, builders, disinfectingagents, enzymes, bleaching agents, finishing agents, preservatives andmixtures thereof.
 13. The composition of claim 1, wherein thenanoparticle is present in an amount from 1.2 to 6 wt. %.
 14. Thecomposition of claim 1, wherein the amine or amide is present in anamount from 1.2 to 6 wt. %.
 15. The composition of claim 1, wherein theinorganic nanoparticle has a BET surface area from about 200 to about400 m2/g.
 16. An aqueous composition comprising: colloidal silicananoparticle; an amphoteric polyamine having at least 3 nitrogen atomsand obtained by reacting polyethylenimine and polyacrylic acid; analcohol having 1-4 carbon atoms; an alkylene glycol alkyl ether; amixture of an amine oxide, a C₁₀-C₁₆ alkyl sulfonate, and asulfosuccinate, and sodiummethylglycine, wherein the colloidal silicaand the amphoteric polyamine are present in a 1:1 weight ratio.